Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/02—Monomers containing chlorine
  • C08F214/04—Monomers containing two carbon atoms
  • C08F214/06—Vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
  • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09J127/06—Homopolymers or copolymers of vinyl chloride

Definitions

• Aqueous copolymer dispersions that contain vinyl chloride units, vinyl acetate units and ethylene units are known and described in German Published Application (DOS) Nos. 21 19 549 and 22 52 285, corresponding to U.S. Pat. Nos. 3,639,326 and 3,830,761 respectively.
• DOS German Published Application
• An object of the present invention is to produce copolymer dispersions containing a high proportion of vinyl chloride units in the copolymer, together with vinyl acetate units and ethylene units that can be polymerized to form stable dispersions in an economical manner without the use of auxiliary monomers, that is, without monomers having strongly polar groups, such as, for example, carboxyl groups, sulfonic acid groups, carbonamide groups, or emulsifiers.
• Another object of the present invention is the development of a stable aqueous vinyl chloride copolymer dispersion having a solids content of from 30% to 70% by weight, said dispersion containing a copolymer consisting of
• a further object of the present invention is the development of a process for the production of the above stable, aqueous vinyl chloride copolymer dispersion comprising the steps of polymerizing monomers in such amounts to give said copolymer in sufficient of an aqueous medium to give a final solids content of from 30% to 70% by weight at temperatures of between +10° C. to +85° C.
• a yet further object of the invention is the development of uses of the above stable, aqueous vinyl chloride copolymer dispersion as (a) binders in hydraulically setting building materials, (b) adhesives in combination with acidic hardeners, and (c) as coating agents in combination with aluminum nitrate, chromium nitrate, acidic phosphates and phosphoric acid as hardeners.
• the subject of the invention is stable, aqueous vinyl chloride copolymer dispersions having solids contents of between 30% and 70% by weight, characterized in that the dispersion contains a copolymer comprising
• ethylene units 5% to 30% by weight of ethylene units and, as protective colloid, 2% to 15% by weight, based on the dispersion weight, of one or more polyvinyl alcohols having a saponification number of between 20 and 240 and a polymerization degree of between 300 and 2000.
• the dispersions it is advantageous additionally to copolymerize from 0.5% to 5% by weight of units of olefinically-unsaturated N-methylolamides.
• the present invention relates to a stable aqueous vinyl chloride copolymer dispersion having a solids content of from 30% to 70% by weight, said dispersion containing a copolymer consisting of
• the mentioned monomer compositions are limiting ranges. In many cases it may be of advantage to aim at copolymer dispersions with compositions of 60% to 80% by weight of vinyl chloride units, 8% to 20% by weight of vinyl acetate units, 10% to 25% by weight of ethylene units and 0.5% to 5% by weight of units of olefinically-unsaturated N-methylolamides.
• Olefinically-unsaturated N-methylolamides which may be employed are, for example, selected from the group consisting of N-methylol-alkenoylamide having 3 to 6 carbon atoms in the alkenoyl, N-methylol alkenyl carbamates having 3 to 6 carbon atoms in the alkenyl, Mannich bases thereof, and N-methylol-lower alkyl ethers thereof, such as N-methylolacrylamide, N-methylolmethacrylamide, N-methylol ally carbamate, Mannich bases, and N-methylol ethers of N-methylolacrylamide, N-methylolmethacrylamide or N-methylol allyl carbamate with methyl or isobutyl alcohols.
• the dispersions are produced in heatable and coolable autoclaves fitted with stirrers.
• the necessary quantity of polyvinyl alcohol having a saponification number of between 20 and 240, and having 300 to 2000 monomer units in the polymer molecule, generally 2% to 15% by weight, preferably 2.5% to 12% by weight, calculated on the dispersion, dissolved in water, is placed in the autoclave.
• a single polyvinyl alcohol may be used alone, but, alternatively, mixtures of different polyvinyl alcohols may be used.
• the polymerization is generally carried out with quantities of redox catalyst of between 0.01% and 3% by weight, based on the monomers.
• the total required quantity of the oxidizing component of the catalyst, or most of it, is introduced at the beginning and the polymerization is controlled by metering in the reducing agent. It is also possible, however, in known manner, to introduce the reducing agent at the beginning and control the reaction with the oxidizing agent. Finally, the polymerization may be controlled by the simultaneous metering in of both components. Approximately 0.01% to 0.5%, preferably 0.03% to 0.3%, of reducing agent and 0.01% to 2%, preferably 0.03% to 0.8%, of oxidizing agents are required, all by weight based on the monomers, wherein, depending on the process, the ratio of oxidizing agent to reducing agent is 0.15 to 6.
• oxidizing component of the catalyst examples include ammonium persulfate, potassium persulfate, hydrogen peroxide and t-butyl hydroperoxide.
• reducing component examples include sodium sulfite, sodium metabisulfite, and zinc or sodium formaldehydesulfoxylate.
• H 2 /noble metal salt catalysts with the simultaneous use of amounts of heavy metal salts as activators. Suitable redox catalyst systems are described, inter alia, in "Fundamental Principles of Polymerization", G. G. D'Alelio, John Wiley & Sons Inc., New York 1952, pages 333 ff.
• the ethylene pressure applied is kept constant and varies between 20 and 150 bar depending on the amount of ethylene that is to be incorporated.
• the pressure range preferably used is 35 to 100 bar.
• the necessary pressure is strongly dependent on the viscosity and the stirring effect in the polymerization mixture. The lower the viscosity, the better is the circulation of the substance in the autoclave, and the lower is the ethylene pressure required to incorporate the desired quantity of ethylene into the copolymer, obviously taking into account the copolymerization and solubility parameters.
• the polymerization temperature is 10° C. to 85° C., preferably 20° C. to 50° C.
• the remaining vinyl chloride and vinyl acetate, as well as the 0.5% to 5% by weight of the olefinically-unsaturated N-methylolamides, of which the methylol group may be etherified are added to the reaction vessel, the ethylene pressure being maintained constant.
• the duration of the reaction depends, for example, on the removal of heat, that is to say, the stirring and cooling system, and the desired monomer concentration during polymerization as well as the catalyst system. Generally, polymerization is complete when no further noticeable heat development is ascertainable and when the vinyl acetate monomer concentration has dropped preferably below 1.5%.
• the polymerization is generally complete. Subsequently, the reaction mixture is postpolymerized, by the addition of additional catalyst and by heating, until the vinyl acetate content is less than 0.5%.
• quantities of catalyst of 0.005% to 0.1%, preferably 0.01% to 0.04%, by weight, calculated on the dispersion, of the oxidizing agent and of the reducing agent, are necessary.
• the dispersions according to the invention are very versatile. They exhibit pigment stability and are excellently suitable as binders in disperse dyestuffs. Their relatively good flame resistance, their high binding capacity and their high saponification resistance render possible the use of the dispersions as binders in hydraulically setting building materials. In addition, they exhibit high adhesive strength and waterproof properties when used in adhesives. In combination with trivalent acidically-hydrolyzing metal salts, favorable pot lives and waterproof properties are obtained. The same applies also in combination with strong protonic acids, such as, for example, phosphoric acid, sulfuric acid, sulfonic acids and hydrochloric acid.
• the hardener additives are, in the case of salts, added to the dispersion in the form of their concentrated aqueous solution (20% to 70% strength) and, in the case of protonic acids (10% to 50% strength), in quantities of 2% to 10% by volume.
• the invention therefore, also resides in the improvement in the process of forming adhesive bonds which comprises applying a vinyl chloride copolymer dispersion in combination with an acidic hardener selected from the group consisting of trivalent acidically-hydrolyzing metal salts and strong protonic acids to the solid surfaces to be bonded and maintaining said solid surfaces together for a time sufficient to form an adhesive bond, the improvement consisting of using the stable, aqueous vinyl chloride dispersion described above, as said vinyl chloride copolymer dispersion.
• an acidic hardener selected from the group consisting of trivalent acidically-hydrolyzing metal salts and strong protonic acids
• the properties of the dispersions when used in gluing wood together, with the addition of trivalent metal inorganic salts, such as, for example, chromium nitrate or aluminum nitrate, were tested according to DIN 68603. According to the highest stress classes of this standard, the adhesive strength is judged after relatively long storage in cold water and/or relatively long storage in boiling water (storage sequence No. 9 of the standard B4/9). A further important value which characterizes the use properties of dispersion adhesives in combination with inorganic salts is the pot life. This should, for use in certain adhesive applications, be longer than one week. These conditions are in some cases even considerably exceeded by the adhesives used in combination with hardener additives.
• trivalent metal inorganic salts such as, for example, chromium nitrate or aluminum nitrate
• emulsifiers are, inter alia, aliphatic ethers of polyoxyethylene, such as, for example, polyoxyethylene-lauryl ether, and polyoxyethylene-oleyl ether, as well as polyoxyethylene-alkaryl ether, such as polyoxyethylene-octylphenyl ether, polyoxyethylene-nonylphenyl ether, etc.
• polyoxyethylene glycol esters and amides such as, for example, esters with higher fatty acids such as the laurate, oleate and isononate and N-polyoxyethylene lauramide.
• Block polymers of ethylene oxide and propylene oxide may also be co-used. Also it is frequently advantageous to co-use anti-foaming agents in quantities of 0.05% to 0.3% by weight of the active substance.
• the present invention also resides in the improvement in the process of forming bonds comprising allowing a mixture of hydraulically-setting binders and vinyl chloride copolymer dispersions to harden, the improvement consisting of using the stable, aqueous vinyl chloride dispersion described above as said vinyl chloride dispersion.
• acidic trivalent metal salts or, alternatively, strong protonic acids are added.
• acidic salts are trivalent metal salts selected from the main and subsidiary group of the Periodic Table of the elements, with strong protonic acids.
• Preferred hardeners in this connection are acidic phosphates, phosphoric acid, aluminum nitrate and chrominum (III) nitrate.
• These coating agents consisting of dispersion and hardener have favorable pot lives and have a corrosion-inhibiting action on, for example, iron, combined with excellent adhesion.
• the hardeners are, in the case of salts, added in the form of their concentrated aqueous solution or, in the case of protonic acids, in semi-concentrated form in quantities of 2% to 8% by weight.
• An inorganic setting material such as hydraulic cement, Portland cement, natural cement (Roman cement) or aluminous cement is used as a mortar binder.
• Customary cement additives such as gypsum, gypsum mortar, calcium phosphate, lime or other such calcium-containing binders, magnesium oxychloride, magnesite or other magnesium-containing or oxy-salt compositions or other similar setting inorganic substances, as used as binders for unmodified concrete and mortar compositions, may optionally be added.
• Sand, stones, concrete, ballast, pebbles, granite, carborundum, aluminum oxide, emery, marble chips, sawdust, slag, asbestos, mica, talcum, flint stones or synthetic products, such as, for example, pulverized ceramic materials, may be added as customary aggregates.
• water-condensable ureaformaldehyde resins or heat-hardenable melamine-formaldehyde resins can be added to the latex coating compositions.
• Pigments such as, for example, clays, aluminum silicates, calcium carbonate, magnesium carbonate, mica, talcum, diatomaceous earth or titanium oxide, zinc phosphate, zinc chromates, iron oxide and chromium oxide, may likewise be added. In this case alkaline and carbonate-containing products may obviously only be added if no acidic hardeners are added.
• processing auxiliaries such as thickeners, coalescence auxiliaries, fillers and reinforcing agents, plasticizers, levelling agents and diluents, antioxidants and stabilizers, or fungicides, may also be co-used.
• the coating agents are suitable as protective or decorative coverings for, for example, metal, wood or mineral surfaces.
• Suitable plasticizers are, for example, butoxyethoxyethyl acetate, acetyl ricinoleic acid butyl ester, diesters of oxalic acid, succinic acid, adipic acid, phthalic acid with aliphatic, branched or unbranched alkanols having 2 to 16 carbon atoms, such as, for example, oxalic acid dibutyl ester, succinic acid dibutyl ester, diisobutyl phthalate, dioctyl phthalate, diisotridecyl phthalate, as well as alkylene glycols, such as, for example, ethylene glycol, hexamethylene glycol, also benzyl alcohol and ester/alcohol mixtures, and diphenoxyphenylformal.
• Organic solvents which are aromatic hydrocarbons or aliphatic hydrocarbons may also be added.
• the dispersion obtained had a solids content of 51.8% by weight, a viscosity, measured in the Epprecht Rheometer stage C III, of 5900 m.Pa.s. and a minimum film-forming temperature of 20° C.
• the dispersion had a polymeric composition of 16.7% ethylene, 70% vinyl chloride, and 13.3% vinyl acetate.
• the dispersion is freeze-resistant, pigment-stable and shear-stable and has good strength values. After the addition of 2% by weight of butoxyethoxyethyl acetate to the dispersion, the tear strength of the film was approximately 12.5 N/mm 2 with an elongation-at-break of approximately 350%.
• the anti-foaming agent consists of 94% by weight of dimethylpolysiloxane having a viscosity of more than 20 centistokes at 25° C., and 6% by weight of finely divided silica. With a plastics/cement factor of 0.05 and a water/cement factor of 0.48, the following values were ascertained:
• Example 1 275 gm each of polyvinyl alcohols having a saponification number of about 70 and viscosities of 13 and 6 mPa.s, respectively, were dissolved, together with the catalyst, in water as in Example 1.
• the processing conditions are the same as in Example 1 except that at the same time as the vinyl chloride/vinyl acetate was metered in, a solution of 50 gm of N-methylol-acrylamide in 100 cm 3 of water/methanol (1:1) was added.
• the processing conditions are the same as in Example 2 except that double the amount of N-methylolacrylamide and 440 gm of a mixture of polyvinyl alcohols having a saponification number of 140 were used.
• 140 gm of polyvinyl alcohol having a Hoppler viscosity of 13 m.Pa.s. and 300 gm having a Hoppler viscosity of 5 m.Pa.s. were used.
• the dispersion so produced was freeze-resistant, pigment-stable and shear-stable, had a solids content of 53.2% by weight and a viscosity measured in the Epprecht Rheometer (stage C III) of 11700 m.Pa.s.
• Aluminum nitrate (5% by volume of a 70% aqueous solution.
• the method of operation was the same as in Example 3 except that polyvinyl alcohols having a saponification number of 20 were used.
• the Hoppler viscosities of the polyvinyl alcohols used were 13 and 5 m.Pa.s. respectively.
• the reaction was controlled by the addition of sodium formaldehydesulfoxylate. After 14 hours, the polymerization was complete, the product was adjusted to a pH of 7 with ammonia, the pressure was released, and post-polymerization and degassing were carried out.
• the dispersion obtained had a solids content of 52.5, a polymeric composition of 16.2% ethylene, 68% vinyl chloride, 13% vinyl acetate and 2.8% N-methylolacrylamide, a viscosity (Rheometer C III) of 2500 m.Pa.s. and a minimum film-forming temperature of 20° C. It was shear-stable, pigment-stable and freeze-resistant and, in the non-cross-linked state, had a tear strength of 18 N/mm 2 with an elongation-at-break of approximately 290%.
• the pot life was more than 20 days.
• the polymerization was carried out in an analogous manner to that used in Example 3, except that a polyvinyl alcohol having a saponification number of 200 was used.
• the solids content of the dispersion was 52.9%, the viscosity (Rheometer C III) 7300 m.Pa.s., and the minimum film-forming temperature 25° C.
• the pigment-stable and shear-stable dispersion had a K-value of 63.
• the solids content of the dispersion was 54.1, the viscosity (Rheometer C III) 4750 m.Pa.s. and the minimum film-forming temperature 18° C.
• the dispersion was freeze-resistant, pigment-stable and shear-stable.
• the solids content was 53.1%, the viscosity (Rheometer C III) 2800 m.Pa.s., and the minimum film-forming temperature 14° C.
• the dispersion was freeze-resistant, pigment-stable and shear-stable.
• the pot life was 25 days.
• the solids content of the dispersion was 53.9% the viscosity (Rheometer C III) 3400 m.Pa.s., and the minimum film-forming temperature 16° C.
• the polymerization was carried out in a manner analogous to that used in Example 5, except that, instead of 175 gm of N-methylolacrylamide, 175 gm of N-methylolallyl carbamate were co-polymerized.
• the product had a solids content of 51.4%, a viscosity (Rheometer C III) of 2100 m.Pa.s., and a minimum film-forming temperature of 19° C.
• the dispersion was freeze-resistant, pigment-stable and shear-stable.

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• Wood Science & Technology (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Adhesives Or Adhesive Processes (AREA)
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• 1977
  • 1977-08-01 DE DE19772734656 patent/DE2734656A1/de not_active Withdrawn
• 1978
  • 1978-06-12 US US05/914,623 patent/US4189415A/en not_active Expired - Lifetime
  • 1978-07-28 IT IT50519/78A patent/IT1106621B/it active
  • 1978-07-31 AT AT0556078A patent/AT363685B/de active
  • 1978-07-31 CH CH818678A patent/CH636891A5/de not_active IP Right Cessation
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  • 1978-08-01 EP EP78100561A patent/EP0000590B1/de not_active Expired
  • 1978-08-01 JP JP9320778A patent/JPS5426892A/ja active Granted
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• 1980
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